You can make the ball roll with a Driver, first - this is what you should already have setuped, make sure the ball's Follow Path constraint option Follow Curve is set:
Add single driver to the X axis rotation field (RMB on field > Add Single Driver R)
Setup the driver like this (scripted type, no variables), also make sure Auto Run Python Scripts in User_Preferences > File is enabled:
Lets add a driver variable for the curve evaluation time, call the variable "eval_time", in the Prop field put the curve and Path is
Now its time for the driver expression. You will need to know the ball's diameter and the curve's length.
diameter you get from ball's dimensions in properties panel N:
curve's length you get from running this script with curve selected:
orig = bpy.context.active_object.name
bpy.ops.object.transform_apply(location=True, rotation=True, scale=True)
bm = bmesh.new()
edge_length = 0
for edge in bm.edges:
edge_length += edge.calc_length()
bpy.context.window_manager.clipboard = str(round(edge_length,3))
bpy.context.scene.objects.active = bpy.context.scene.objects[orig]
bpy.context.object.select = True
It will calculate the length and store it in the clipboard, you can then paste it with Ctrl+V.
The driver expression is: -2 * curve_length / diameter * ( eval_time / eval_max ):
Let's break the expression down:
(eval_time/eval_max) is the only element that changes and it goes from 0 to 1 as the ball moves along the curve
the rest equates to a number, that says how much has the ball turn to rotate along the whole path
If the ball turns 1 complete rotation (360°), it will travel pi*diameter units.
So to cover the path it needs curve_length / pi*diameter of full rotations.
The catch is that driver expects the input in radians, not degrees. So a full rotation of 360° is 2*pi radians.
(2pi) * curve_length / pidiameter, we can simplify and remove pi
The last thing is the minus in front of the expression (-), this is to influence which direction we want the ball to roll. You can use the right hand rule to see what rotation is positive, and what negative (thumb in axis direction, fingers point in positive rotation direction).
Now the ball will roll accordingly to your curve's Evaluation Time: